Monoazo hetero-oxygen compounds



Patented Dec. 18, 1945 Jakob Danuser,

Capeller,

Basel, Switzerland No Drawing. Applicati Serial No. 502,028. In

Arlesheim, Riehen, Switzerland, firm Society of Chemical Industry and Rudolf von assignorsto the in Basle,

on September 11, 1943, Switzerland October 12,

Claims. (01. 260-152) when using, as diazotized'amines of the benzene series, amines which contain an O-alky1 group in 4-position to the amino group, there are obv tained :dyestufis, such as the coupling product from diazotized paraanisidine and 'para-cresol, the dyeingspf which on acetyl cellulose possess a fastness to light which is considerably superior to that of the dyeings obtained according to Patent No. 1,765,142. The wet fastness properties of the dyeingsthus obtained, especially their fastness to ironing and their fastness to sublimation, however, do not satisfy present day requirements.

it has now been found that dyestuffs are obtamedin which the excellent fastnless to light of the dyestuffs of Patent No. 1,893,543 is combined with the other good wetfastness propertiesof the, dyeings produced with the dyestuiis obtainable according to Patent No. 1,765,142, if diazo compounds of aromatic amines of the benzeneseries which contain in 4-position tothe amino group an O-alkylene. group linked by its oxygen atom -to the benzene ringwhichalkylene group belongs itself to.a heterocyclic ring fused on in 3- and 4-positions of 'the benzene ring, that part of the heterocyclic ring which'is not fused on at the benzene ring consisting of 2-oxygen atoms and at least 1 and not more than 2 carbon 'atoms. and containing the Z-oxyge'n atoms separated from'each other by at least one carbon atom; are caused to react with hydroxy compounds of the benzene series which couple in ortho position to'the: hydroxyl group.

"The dyestuffs thus obtained correspond to the general formula wherein R1 stands for'an aromatic nucleus of the benzene series which contains in 4-position to the azo group an O-alkylene group linked by its oxygen atom to the benzene ring which alkylene group belongs to a heterocyclic ring fused on in 3- and 4-positions of the benzene ring that part of the heterocyclic ring which is not fused on at the benzene ring consisting of 2 oxygen atoms ogous processes described there.

- 4-nitro-pyrocatechin and at least 1 and not more than 2 carbon atoms 'and containing the 2-oxygen atoms separated from each other by at least one carbon atom and R2 stands fora benzene nucleus which contains a hydroxyl group in ortlio-position to the azo group, and carries a substituent in 4-position to this hydroxyl group which causes coupling in 2-position.

The new dyestuffs are yellow to brown powders which are sparingly soluble in water, but are soluble in organic solvents, for example acetic ether, to yellow to orange solutions. From a finely dispersed aqueous suspension they have an excellent afiinity for esters and, ethers of cellulose, especially acetate rayon, and they may further be used for dyeing synthetic fibers of animal character, such as superpolyamides and superpolyurethanes. The valuable properties of the new dyestuifs are surprising because it was not to be expected that by using the ethers of Patent No. 1,893,543 converted into heterocyclic rings, dyestuffs of equal affinity could be obtained,

- and that the dyeingsobtained therefrom would possess good wet fastness properties in spite of the remaining ethereal character of the dyestuffs.

The aromatic amines of the benzene series used in this specification Whose nuclear carbon atoms standing in 3- and 4-positions to the amino group 'are constituents of the above characterized heterocyclic ring, are known in the literature or may be produced according to anal- The corresponding nitro compounds are known in many instances; these may be converted into the amino compounds according to known methods. Among these compounds mention is made of the 4-aminopyrocatechinmethylene ether, obtainable by reduction from l-nitropyrocatechin methylene ether (cf. Beilstein, 4th Edition, vol. 19, pages 20) of the 4-nitro-5-brompyrocatechin methylene ether (cf. Berichte, Vol. 24;"page 2593, of 71891) which is converted by reduction into the 4-amino-5-bromopyrocatechin methylene ether; of the ethylene ether (cf.' Annalen, vol. 280, page 206 of 1894), obtainable by reduction from the 4- aminopyrocatechin ethylene ether; of the methylene ether of the 5-amino-2- hydroxy benzyl alcohol obtainable by treating para-nitrophenol with formaldehyde and sulfuric acid (of. Annalen, vol. 330, page 91 of 1904) and subsequent reduction of the nitro group; of the methylene ether of 5-amino-2-hydroxy-3- methylbenzyl alcohol, which may be produced over 5-nitro-2-hydroxy-S-methylbenzyl alcohol methylene ether (cf.Annalen, vol. 330, page methylbenzene, 1 hydroXy-3-methyl-4-acetylaminobenzene, 1-hydroxy-4 methyl-3-acetylaminobenzene, 1-hydro-xy-4-methy1-3 aminobenzene, 1-hydroxy-4-methoxybenzene, and the like.

The following examples illustrate the invention, but are not to be regarded as limiting it in any way, the parts being by weight:

Example 1 15.1 parts of l-aminopyrocatechin ethylene ether are suspended in about 100 parts of water and diazotized with 25 parts of hydrochloric acid of 30 per cent. strength and '7 parts of sodium nitrite. The cold solution of the diazonium compound is added to a cold solution containing 10.8 parts of l-hydroxy-l-methylbenzene, 10 parts of sodium hydroxide cent. strength and 15 parts of sodium carbonate.

The dyestufr of the formula GE's-0 N=N (LHz-O is precipitated and, when coupling is complete, filtered and washed. When dry it is a yellow powder which dissolves in organic solvents, such as alcohol, acetic ether, to a yellow solution. When ground with a dispersing agent, for example sulfite cellulose waste liquor, there is obtained a fine paste which yields a fine suspension in water, from which acetate rayon is dyed fast yellow shades.

The procedure is similar with the other diazotizing components cited in the introduction, for

example 4-aminopyrocatechin methylene ether. There is then obtained a product of the formula Instead of 1-hydroxy-4-methylbenzene there may also be used the other hydroxybenzenes named in the introduction, for example l-hydroxy-3z4-dimethylbenzene or 1-hydroxy-3- chloro-4-methylbenzene.

Example 2 15.1 parts of the methylene ether of 5-amino- 2-hydroxybenzyl alcohol are diazotized in aqueous solution with 25 parts of hydrochloric acid of 30 per cent. strength and 7 parts of sodium nitrite. A solution is prepared from 10.8 parts of 1-hydroxy-4-methylbenzene in 10 parts of sodium hydroxide solution of 30 per cent strength and parts of sodium carbonate and about 100 solution of 30 per parts of water. This solution cooled with ice is mixed with the diazonium solution obtained above and the whole is stirred until the formation of dyestufi is complete. The dyestuff is then filtered and washed.

The dyestuff Of the formula CH3 has similar properties like the dyestufi of Example 1. It dyes acetate rayon from a fine suspension pure yellow shades of good fastness properties. A similar dyestuif is formed from the diazotized 5-amino-2-hydroxy 3-methoxybenzyl alcohol which corresponds to the formula OH CHI I 0 OH: CH:

Ewample 3 10 parts of the dyestuff of the first paragraph of Example 2 are ground to a homogeneous paste containing 20 per cent. of dyestuff with addition of a suitable dispersing agent,-such as Turkey red oil, sulfite cellulose waste liquor, sulfonation products of the residues of the benzalde-manufacture. One part of this paste is intimately mixed with 10 parts of water of 50 C. and so many parts of a concentrated soap solution that the dyebath prepared therefrom corresponds to a soap solution of 0.2 per cent. strength. The mixture is then diluted with cold water to about 300 parts of water. 10 parts of acetate rayon yarn are introduced into the emulsion thus prepared and handled therein, the dyebath is heated within hour to 75 C. and dyeing is continued for about hour at this temperature. The material is then rinsed and brightened as usual. There are obtained fast vivid yellow shades which are not phototropic.

What we claim is:

1. The dyestuffs of the general formula wherein R1 stands for an aromatic nucleus of the benzene series which contains in 4-position to the azo group an O-alkylene group linked by its oxygen atom to the benzene ring, which alkylene group belongs to a heterocyclic ring fused on in 3- and. 4-positions, that part of the heterocyclic ring which is not fused on consisting of 2 oxygen atoms and at least one and not more than 2 carbon atoms and containing the two oxygen atoms separated from each other by at least one carbon atom, and R2 stands for a benzene nucleus which contains a hydroxyl group in ortho-position to the azo group and carries in 4-position to this hydroxyl group a substituent selected from the group consisting of methyl, methoxy and acetylam no.

2. The dyestufis oi the formula The y t f the formula OCH CH (3g /0 a l O\ N=N-R1 5 (3H, CH2 7 0 N: wherein R2 stands for a. benzene nucleus which contains a hydroxyl group in ortho-position to OH the azo group and carries in 4-position to this 10 hydroxyl group a substituent selected from the The dyestufi of the formula group consisting of methyl, methoxy and acetyl- OH amino. t

s. The dyestufi of the formula. V on,

CH 1111 0 O CH: CH: J) N: JAKOB DANUSER.

RUDOLF vow CAPELLER. 

